Energy-consistent time integration for nonlinear viscoelasticity

This work is concerned with the numerical solution of the evolution equations of thermomechanical systems, in such a way that the scheme itself satisfies the laws of thermodynamics. Within this framework, we present a novel integration scheme for the dynamics of viscoelastic continuum bodies in isothermal conditions. This method intrinsically satisfies the laws of thermodynamics arising from the continuum, as well as the possible additional symmetries. The resulting solutions are physically accurate since they preserve the fundamental physical properties of the model. Furthermore, the method gives an excellent performance with respect to robustness and stability. Proof for these claims as well as numerical examples that illustrate the performance of the novel scheme are provided

Diseño y síntesis de materiales nanoestructurados basados en aluminatos de estroncio con propiedades fotoluminiscentes

Durante la última década, se han llevado acabo numeroso estudios sobre la síntesis de materiales fotoluminiscentes sub-micrónicos, en gran medida, al amplio número de aplicaciones que demandan este tipo de materiales. En concreto dentro de los materiales fosforescentes o también denominados materiales con una prolongada persistencia de la luminiscencia, los estudios se han enfocado en la matriz de SrAl2O4 dopada con Europio (Eu2+) y Disprosio (Dy3+) dado que tiene mayor estabilidad y persistencia de la fosforescencia con respecto a otras matrices. Estos materiales se emplean mayoritariamente en pinturas luminiscentes, tintas, señalización de seguridad pública, cerámicas, relojes, textiles y juguetes fosforescentes. Dado al amplio campo de aplicación de los SrAl2O4:Eu, Dy, se han investigado múltiples rutas de síntesis como la ruta sol-gel, la síntesis hidrotermal, la síntesis por combustión, la síntesis láser y la síntesis en estado sólido con el fin de desarrollar un método eficiente y que sea fácilmente escalable. Sin embargo, en la actualidad el método que se emplea para el procesamiento a nivel industrial de los materiales basados en aluminato de estroncio es la síntesis por estado sólido, que requiere de temperaturas de entre 1300 a 1900oC y largos tiempos de procesamiento. Además el material obtenido tiene un tamaño de partícula de 20 a 100 μm; siendo este tamaño restrictivo para el empleo de este tipo de material en determinadas aplicaciones. Por tanto, el objetivo de este trabajo es el desarrollo de nuevas estrategias que solventen las actuales limitaciones. Dentro de este marco se plantean una serie de objetivos específicos: Estudio de los parámetros que gobiernan los procesos de reducción del tamaño de partícula mediante molienda y su relación en la respuesta fotoluminiscente. Estudio de la síntesis por combustión de SrAl2O4:Eu, Dy, evaluando el efecto de la temperatura y la cantidad de combustible (urea) en el proceso para la obtención de partículas cristalinas minimizando la presencia de fases secundarias. Desarrollo de nuevas rutas de síntesis de SrAl2O4:Eu, Dy empleando el método de sales fundidas. Determinación de los mecanismos de reacción en presencia de la sal fundida en función de los parámetros de proceso que comprende la relación de sales y reactivos, la naturaleza de la alúmina y su tamaño, la temperatura y atmósfera de tratamiento. Mejora de la eficiencia de los procesos de síntesis para obtener productos con propiedades finales óptimas en procesos factibles industrialmente para su transferencia tecnológica. Es este trabajo han sido evaluados los efectos de diferentes procesos de molienda para la reducción del tamaño de partícula del material de SrAl2O4:Eu, Dy comercial. En el proceso de molienda en medio húmedo por atrición se observa la alteración de la estructura cristalina del material debido a la reacción de hidrólisis generada incluso empleando como medio líquido etanol absoluto. Con el fin de solventar las desventajas de la molienda en medio húmedo se llevo a cabo un estudio de la molturación en seco del material. La molturación en seco de alta energía reduce significativamente el tamaño medio de partícula. Sin embargo, procesos de molienda superiores a una duración de 10 minutos ocasionan un aumento del estado de aglomeración de las partículas y disminuyen drásticamente la respuesta fotoluminiscente del material. Por tanto, se lleva a cabo un proceso de molienda en seco de baja energía. Mediante este método se consigue reducir el tamaño medio de partícula, d50=2.8 μm, y se mejora la homogeneidad de la distribución del tamaño de partícula evitando la amorfización del material. A partir de los resultados obtenidos mediante difracción de rayos X y microscopia electrónica de barrido se infiere que la disminución de la intensidad de la fotoluminiscencia después de la molienda en seco de alta energía con respecto al material inicial se debe principalmente a la reducción del tamaño de cristalito. Se observan menores variaciones en la intensidad de la fotoluminiscencia cuando se emplea un método de molienda de baja de energía ya que en estos procesos se preserva el dominio cristalino y se reduce la amorfización significativamente. Estos resultados corroboran que la intensidad de la fotoluminiscencia y la persistencia de la luminiscencia de los materiales de SrAl2O4:Eu2+, Dy3+ dependen extrínsecamente de la morfología de las partículas, del tamaño de partícula, el tamaño de grano, los defectos superficiales e intrínsecamente del tamaño de cristalito. Siendo las características intrínsecas las que dominan con respecto a las extrínsecas y por tanto tienen mayor relevancia en la respuesta fotoluminiscente. Mediante síntesis por combustión se obtuvieron láminas nanoestructuradas de SrAl2O4:Eu, Dy de ≤1 μm de espesor. La cantidad de combustible, urea, en la reacción influye significativamente en la formación de determinadas fases cristalinas. Para la síntesis del material de SrAl2O4:Eu, Dy es necesario incluir un contenido de urea mayor que el estequiométrico (siendo m=1 la relación estequiométrica). La incorporación de un exceso de urea (m>1) requiere de la presencia de un agente oxidante interno, HNO3, para que la reacción tenga lugar. El empleo de un mayor contenido de urea como combustible permite una quelación efectiva de los cationes en el sistema y la creación de las condiciones reductoras para obtener un material de mayor cristalinidad y con mejores propiedades fotoluminiscentes. El material de SrAl2O4:Eu, Dy sintetizado a una temperatura de ignición de 600oC tiene un tamaño medio 5-25 μm con un espesor de ≤1 μm. Mediante procesos de molturación en seco de baja energía es posible disminuir el tamaño medio de partícula ≈2 μm y homogenizar la distribución del tamaño de partícula pero hay un deterioro asociado de la respuesta luminiscente. Sin embargo, se puede mejorar la respuesta fotoluminiscente empleando un tratamiento térmico posterior a 900oC N2-H2 durante 1 hora que no supone un aumento del tamaño de partícula pero si permite aumentar el tamaño de cristalito y la reducción del Eu3+ a Eu2+. Con respecto a la respuesta fotoluminiscente, se obtiene valores de la intensidad de la fotoluminiscencia entre un 35%-21% con respecto a la intensidad de un material comercial de referencia. Además la intensidad inicial del decaimiento de la fosforescencia es un 20% de la intensidad del material de referencia. Por tanto, teniendo en cuenta estos resultados, es necesario explorar otros métodos de síntesis para la obtención de los materiales bajo estudio. Por esta razón, en este trabajo se desarrollo una ruta de síntesis novedosa para sintetizar SrAl2O4:Eu, Dy mediante el método de sales fundidas para la obtención de materiales de gran cristalinidad con tamaños de cristalito del orden nanométrico. Se empleo como sal fundente la mezcla eutéctica de NaCl y KCl, denominada (NaCl-KCl)e. La principal ventaja de la incorporación de la mezcla es el incremento la reactividad del sistema, reduciendo la temperatura de formación del SrAl2O4 y la duración del tratamiento térmico en comparación con la síntesis en estado sólido. La formación del SrAl2O4 es favorecida ya que se aumenta la difusión de los cationes de Sr2+ en el medio líquido. Se emplearon diferentes tipos de Al2O3 para evaluar el papel del tamaño de partícula y su naturaleza en la reacción asistida por sales fundidas y por tanto en la morfología y propiedades del producto final. Se obtuvieron partículas de morfología pseudo-esférica de tamaño ≤0.5 μm al emplear como alúmina precursora partículas sub-micrónicas ( 0.5 μm Al2O3, 0.1 μm Al2 O3 y γ-Al2O3). El mecanismo de reacción que tiene lugar se asocia a procesos de disolución-precipitación que dominan al emplear partículas de alúmina pequeñas y reactivas. Mientras al emplear una alúmina de 6 μm Al2O3 prevalecen los procesos de crecimiento cristalino siguiendo un patrón o plantilla debido a la menor reactividad del sistema. La nucleación y crecimiento de nanocristales de SrAl2O4:Eu, Dy se genera sobre la superficie de la alúmina que actúa como soporte. De esta forma se desarrolla una estructura del tipo coraza-núcleo («core-shell» en inglés) donde la superficie externa está formada por los cristales fosforescentes de SrAl2O4 y el núcleo está formado por alúmina. Las partículas obtenidas tienen una respuesta fotoluminiscente diferente en función de la morfología final obtenida. La optimización de la relación Al2O3/SrO del material de SrAl2O4:Eu, Dy sintetizado a partir de la alúmina de 6 μm permite reducir las fases secundarias y la concentración de dopantes manteniendo la respuesta fotoluminiscente. Comparativamente con un material comercial de SrAl2O4:Eu, Dy de referencia, se han alcanzado valores de la intensidad de la emisión de hasta el 90% y de la intensidad inicial de las curvas de decaimiento de la luminiscencia de un 60% para el material sintetizado por sales fundidas que tiene un tamaño medio ≤ 10μm. Por otra parte, es necesario tener en cuenta que el SrAl2O4 tiene dos polimorfos, la fase monoclínica que es estable a temperaturas inferiores a 650oC y la fase hexagonal, fase de alta temperatura, estable a temperaturas superiores de 650oC. Se ha determinado que fase monoclínica presenta propiedades luminiscentes, sin embargo existen discordancias a cerca de las propiedades luminiscentes de la fase hexagonal. Mediante la síntesis por sales fundidas es posible estabilizar la fase hexagonal empleando como alúmina precursora γ-Al2O3 y un exceso de Al2O3 (Al2O3/SrO:2). La estabilización de la fase hexagonal a temperatura ambiente se produce cuando el tamaño de los cristales de SrAl2O4 es ≤20 nm. Además se observó que la fase hexagonal presenta respuesta fotoluminiscente. El diseño de materiales de SrAl2O4:Eu,Dy nanoestructurados permite modular la morfología del material y por tanto la intensidad de la de la fotoluminiscencia y la persistencia de la luminiscencia. La disminución de los materiales precursores, la temperatura y el tiempo de tratamiento significa la reducción de los costes económicos del material. De ahí la viabilidad de los materiales de SrAl2O4:Eu,Dy obtenidos mediante los procesos de síntesis propuestos en esta memoria de tesis para su posterior escalado industrial. ABSTRACT The synthesis of sub-micron photoluminescent particles has been widely studied during the past decade because of the promising industrial applications of these materials. A large number of matrices has been developed, being SrAl2O4 host doped with europium (Eu2+) and dysprosium (Dy3+) the most extensively studied, because of its better stability and long-lasting luminescence. These functional inorganic materials have a wide field of application in persistent luminous paints, inks and ceramics. Large attention has been paid to the development of an efficient method of preparation of SrAl2O4 powders, including solgel method, hydrothermal synthesis, laser synthesis, combustion synthesis and solid state reaction. Many of these techniques are not compatible with large-scale production and with the principles of sustainability. Moreover, industrial processing of highly crystalline powders usually requires high synthesis temperatures, typically between 1300 a 1900oC, with long processing times, especially for solid state reaction. As a result, the average particle size is typically within the 20-100 μm range. This large particle size is limiting for current applications that demand sub-micron particles. Therefore, the objective of this work is to develop new approaches to overcome these limitations. Within this frame, it is necessary to undertake the following purposes: To study the parameters that govern the particle size reduction by milling and their relation with the photoluminescence properties. To obtain SrAl2O4:Eu, Dy by combustion synthesis, assessing the effect of the temperature and the amount of fuel (urea) to synthesize highly crystalline particles minimizing the presence of secondary phases. To develop new synthesis methods to obtain SrAl2O4:Eu, Dy powders. The molten salt synthesis has been proposed. As the method is a novel route, the reaction mechanism should be determine as a function of the salt mixture, the ratio of the salt, the kind of Al2O3 and their particle size and the temperature and the atmosphere of the thermal treatment. To improve the efficiency of the synthesis process to obtain SrAl2O4:Eu, Dy powders with optimal final properties and easily scalable. On the basis of decreasing the particle size by using commercial product SrAl2O4:Eu2+, Dy3+ as raw material, the effects of different milling methods have been evaluated. Wet milling can significantly alter the structure of the material through hydrolysis reaction even in ethanol media. For overcoming the drawbacks of wet milling, a dry milling-based processes are studied. High energy dry milling process allows a great reduction of the particle size, however milling times above 10 min produce agglomeration and accelerates the decrease of the photoluminescence feature. To solve these issues the low energy dry milling process proposed effectively reduces the particle size to d50=2.8 μm, and improves the homogeneity avoiding the amorphization in comparison with previous methods. The X-ray diffraction and scanning electron microscope characterization allow to infer that the large variations in PL (Photoluminescence) values by high energy milling process are a consequence mainly of the crystallite size reduction. The lesser variation in PL values by low energy milling proces is related to the coherent crystalline domain preservation and the unnoticeable amorphization. These results corroborate that the photoluminescence intensity and the persistent luminescence of the SrAl2O4:Eu2+, Dy3+ powders depend extrinsically on the morphology of the particles such as particle size, grain size, surface damage and intrinsically on the crystallinity (crystallite size); being the intrinsically effects the ones that have a significant influence on the photoluminescent response. By combustion method, nanostructured SrAl2O4:Eu2+, Dy3+ sheets with a thickness ≤1 μm have been obtained. The amount of fuel (urea) in the reaction has an important influence on the phase composition; urea contents larger than the stoichiometric one require the presence of an oxidant agent such as HNO3 to complete the reaction. A higher amount of urea (excess of urea: denoted m>1, being m=1 the stoichiometric composition) including an oxidizing agent produces SrAl2O4:Eu2+,Dy3+ particles with persistent luminescence due to the effective chelation of the cations and the creation of suitable atmospheric conditions to reduce the Eu3+ to Eu2+. Therefore, optimizing the synthesis parameters in combustion synthesis by using a higher amount of urea and an internal oxidizing agent allows to complete the reaction. The amount of secondary phases can be significantly reduced and the photoluminescence response can be enhanced. This situation is attributed to a higher energy that improves the crystallinity of the powders. The powders obtained have a particle size c.a. 5-25 μm with a thickness ≤1 μm and require relatively low ignition temperatures (600oC). It is possible to reduce the particle size by a low energy dry milling but this process implies the decrease of the photoluminescent response. However, a post-thermal treatment in a reducing atmosphere allows the improvement of the properties due to the increment of crystallinity and the reduction of Eu3+ to Eu2+. Compared with the powder resulted from solid state method (commercial reference: average particle size, 20 μm and heterogeneous particle size distribution) the emission intensity of the powder prepared by combustion method achieve the values between 35% to 21% of the reference powder intensity. Moreover, the initial intensity of the decay curve is 20% of the intensity of the reference powder. Taking in account these results, it is necessary to explore other methods to synthesize the powders For that reason, an original synthetic route has been developed in this study: the molten salt assisted process to obtain highly crystalline SrAl2O4 powders with nanometric sized crystallites. The molten salt was composed of a mixture of NaCl and KCl using a 0.5:0.5 molar ratio (eutectic mixture hereafter abbreviated as (NaCl-KCl)e). The main advantages of salt addition is the increase of the reaction rate, the significant reduction of the synthesis temperature and the duration of the thermal treatment in comparison with classic solid state method. The SrAl2O4 formation is promoted due to the high mobility of the Sr2+ cations in the liquid medium. Different kinds of Al2O3 have been employed to evaluate the role of the size and the nature of this precursor on the kinetics of reaction, on the morphology and the final properties of the product. The SrAl2O4:Eu2+, Dy3+ powders have pseudo-spherical morphology and particle size ≤0.5 μm when a sub-micron Al2O3 ( 0.5 μm Al2O3, 0.1 μm Al2O3 and γ-Al2O3) has been used. This can be attributed to a higher reactivity in the system and the dominance of dissolution-precipitation mechanism. However, the use of larger alumina (6 μm Al2O3) modifies the reaction pathway leading to a different reaction evolution. More specifically, the growth of SrAl2O4 sub-micron particles on the surface of hexagonal platelets of 6μm Al2O3 is promoted. The particles retain the shape of the original Al2O3 and this formation process can be attributed to a «core-shell» mechanism. The particles obtained exhibit different photoluminescent response as a function of the final morphology of the powder. Therefore, through this study, it has been elucidated the reaction mechanisms of SrAl2O4 formation assisted by (NaCl-KCl)e that are governed by the diffusion of SrCO3 and the reactivity of the alumina particles. Optimizing the Al2O3/SrO ratio of the SrAl2O4:Eu, Dy powders synthesized with 6 μm Al2O3 as a precursor, the secondary phases and the concentration of dopant needed can be reduced keeping the photoluminescent response of the synthesized powder. Compared with the commercial reference powder, up to 90% of the emission intensity of the reference powder has been achieved for the powder prepared by molten salt method using 6μm Al2O3 as alumina precursor. Concerning the initial intensity of the decay curve, 60% of the initial intensity of the reference powder has been obtained. Additionally, it is necessary to take into account that SrAl2O4 has two polymorphs: monoclinic symmetry that is stable at temperatures below 650oC and hexagonal symmetry that is stable above this temperature. Monoclinic phase shows luminescent properties. However, there is no clear agreement on the emission of the hexagonal structure. By molten salt, it is possible to stabilize the hexagonal phase of SrAl2O4 employing an excess of Al2O3 (Al2O3/SrO: 2) and γ-Al2O3 as a precursor. The existence of nanometric crystalline domains with lower size (≤20 nm) allows the stabilization of the hexagonal phase. Moreover, it has been evidenced that the hexagonal polymorph exhibits photoluminescent response. To sum up, the design of nanostructured SrAl2O4:Eu2+, Dy3+ materials allows to obtain different morphologies and as consequence different photoluminescent responses. The reduction of temperature, duration of the thermal treatment and the precursors materials needed imply the decrease of the economic cost of the material. Therefore, the viability, suitability and scalability of the synthesis strategy developed in this work to process SrAl2O4:Eu2+, Dy3+ are demonstrated.

Terremoto 2010 en Chile y vivienda social: resultados y aprendizajes para recomendación de políticas públicas

El territorio chileno esta propenso, desde antes que se constituyera como nación, al impacto del comportamiento de la naturaleza que le es inherente y que también le produce daños. Está representado en los seísmos, los más dañinos. Todavía, la sociedad chilena no termina de comprender que esos daños, son parte de un desequilibrio de una convivencia armoniosa entre ella y esa naturaleza, puesto que el ser humano que vive y habita sobre ella, también lo es. Así entonces, cada vez que el territorio y su espacio son remecidos por los seísmos, la naturaleza, manifestada en la sociedad, adquiere nuevos aprendizajes para mejorar la respuesta al próximo evento. El terremoto 2010 de 8.8° Richter, fue el segundo de mayor magnitud después del otro que hasta ahora, es el más grande del planeta, y que pudo ser medido. Aquel, fue el terremoto de Valdivia de 9,5° Richter, ocurrido el 22 de mayo de 1960. Las sociedades no son estáticas, cambian, son dinámicas. Esta vez el seísmo del 2010, ocurrió en una sociedad que hace ya 35 años, adoptó un modelo de economía de libre mercado. La pobreza que tenía a 1990, era de aproximadamente, un 40%. La del 2010, de un 14%. Durante la dictadura militar hubo otro seísmo de 7,8° Richter, recién instalándose el modelo aludido. El del 2010, permite sacar conclusiones en el contexto de este modelo económico. Los resultados aparentemente son interesantes en cuanto a que hubo pocas víctimas pero por otra parte, hubo un gran daño económico. La tesis profundiza en el impacto del seísmo en la dimensión del parque habitacional construido y de la vivienda social y en los habitantes más pobres y vulnerables. Es la primera investigación sobre seísmos y vivienda social en Chile. Se asume la hipótesis que ciertas variables por una parte, y una cultura antisísmica por otra, están presentes y han penetrado en los sectores populares durante los últimos 50 años y que ello, podría estar en la base de los resultados obtenidos. Se plantea una suerte de “matrimonio bien avenido” entre el habitante y políticas públicas en vivienda. De ello, se derivan recomendaciones para mejorar los avances en el problema investigado que se contextualizan en referencia al marco teórico elaborado. Sin embargo, y no obstante lo investigado, lo ya avanzado no garantiza buenos resultados en el próximo evento, Por ello, los aprendizajes nutren a otros, nuevos, que acompañarán a la sociedad chilena en su esencia e identidad como nación. ABSTRACT Long before its establishment as an independent nation, the Chilean territory has been prone to the impact of nature, which is an inherent and damaging feature of this land. Such an impact is represented by earthquakes, which are regarded as the most damaging natural disasters. Today, the Chilean society is still unable to understand that these impacts are part of an unbalanced coexistence between individuals and nature since human beings, who live and inhabit this space, are also an element of nature. Therefore, each time this territory is hit by earthquakes, nature —represented by society— learns new lessons in order to provide a better response to future events. The 2010 earthquake, which rated 8.8 on the Richter scale, was the second largest earthquake after the most powerful earthquake ever recorded. Such an event was the Valdivia earthquake of May 22, 1960, which rated 9.5 on the Richter scale. Societies are not static as they are changing and dynamic. The 2010 earthquake took place within a context in which society operated under a free market economy model that had been running for 35 years. As of 1990, 40 per cent of the population lived in poverty; in 2010, such a figure was reduced to 14 per cent. Likewise, a magnitude 7.8 quake struck the country during the military regime period in the early days of the above model. The 2010 earthquake allows us to draw some conclusions within the context of this economic model. Results are interesting since there were few fatalities but significant economic loss. This thesis provides insights into the impact of the 2010 earthquake on the housing stock, social housing and those living in poverty and vulnerability. This is the first research on earthquakes and social housing conducted in Chile. The hypothesis is that certain variables and anti-seismic culture have permeated popular segments of the population over the last 50 years. The latter may be at the basis of the results obtained during this research. Likewise, this study proposes a certain “happy marriage” between the inhabitant and public policies on housing. The above offers some recommendations intended to further explore this issue; these suggestions are contextualized according to the theoretical framework developed in this research. However, current progress on this matter does not ensure positive results in the event of an earthquake. This is why these lessons will serve as models for future events, which are intrinsically tied to local society and Chilean identity.

Sistemas urbanos emergentes: procesos informales de gestión y producción de espacio público

Esta investigación analiza la capacidad del urbanismo de albergar sistemas emergentes de gestión urbana. El objetivo de esta tesis es describir estos procedimientos informales, realizando un exhaustivo recorrido a través de diversas experiencias de alteración del modo de gestión urbana al uso, para dar lugar a una sistematización de estos procesos que siente las bases para plantear nuevas formas de gestión urbana. Es decir, el fin no es tanto hacer una clasificación de las intervenciones más relevantes en materia urbana, sino descubrir su estructura, un orden para el desorden, una taxonomía en esas actuaciones que permita reformular las formas actuales de gestión de lo público. Se ha tratado de dibujar un mapa de oportunidades posibles en torno a la gestión del espacio urbano. A través de los procesos estudiados, esta investigación analiza los éxitos y fracasos obtenidos en los últimos cinco años de gestión alternativa de espacios vacantes, buscando extraer formulas susceptibles de incorporarse al modo actual de hacer ciudad. Este estudio pretende abordar un aspecto parcial, aunque fundamental del urbanismo, dando prioridad a lo público, sin la intención de negar el resto de formas del espacio urbano. Se concentra en los parámetros relativos a la interpretación de lo público: desatiende al conjunto urbano para descifrar ese fragmento. Así, el interés principal de esta tesis se concentra en la producción del espacio público. Al entender este ámbito como no exclusivo del urbanismo, otras actividades como el arte, la filosofía, la antropología o la sociología han aportado aspectos fundamentales dentro de esta investigación. De esta forma se ofrece un acercamiento poliédrico desde puntos de vista interdisciplinares, tratando de descubrir con rigor las posibilidades contrastadas de mejora del espacio urbano producido por los procesos emergentes de gestión informal de lo público. Mediante un metodología creada ex profeso (una estructura definida por tres líneas estratégicas: Gobernanza, Complejidad y Cohesión Social, que se desglosan en seis conceptos clave cada una) esta investigación analiza los aspectos relativos a la producción informal del espacio público de los sistemas emergentes. En relación con la Gobernanza, una parte de esta tesis se dedica al estudio de la informalidad, la transversalidad, la apropiación, la participación, la transparencia y las redes. La Complejidad se ha estudiado en su relación con la diversidad urbana, el uso sostenible del espacio público, la reactivación, la producción de espacio público, la ecología urbana y los procesos creativos. Para Cohesión Social se ha investigado la innovación en equipamientos, los procesos bottom-up, el rizoma, la identidad, los sistemas líquidos y el empoderamiento. Esta máquina para analizar se prueba en tres soportes urbanos: la escena urbana, los edificios-contenedores y los vacíos urbanos. Se han estudiado cinco situaciones urbanas en la ciudad de Madrid, seleccionados por ser las prácticas urbanas más relevantes de los últimos cinco años. Si bien este análisis nace de estos cincos casos, el modelo podría ser útil para otras investigaciones interesadas en los aspectos informales de la gestión urbana. Esta investigación se propone reclamar otras dimensiones más innovadoras que, si bien se escapan a los modos habituales de trabajar del urbanista, se revelan intensamente en los modos actuales de reclamar y producir espacio urbano. Se ha pretendido descubrir el espacio urbano como contenedor situacional del sentido público, potencial multiplicador de efectos funcionales como la gestión, la temporalidad, la participación, la rehabilitación, la multiplicidad de usos, la corrección del compacidad; efectos perceptuales y estéticos en la escena urbana; efectos políticos, de formación, de adquisición de poder; efectos sociales como la generación de nuevas redes, la creación de identidades. Se pretende que esta investigación arroje conclusiones que puedan tener aplicabilidad en la gestión y planificación del espacio público de ciudades y entornos urbanos inmersos a procesos semejantes. ABSTRACT This research examines the ability of urban planning to accommodate emerging urban management systems. The purpose of this thesis is to describe such informal procedures, by carrying out an exhaustive review across the different approaches to urban management, in order to systematize them as the basis for new ways of urban management. The aim is not, that is, to classify relevant urban interventions, but to recognize the intrinsic structure, an order for disorder, a taxonomy in those proceedings that could help reformulating existing forms of public management. The attempt has been to draw a map of possible opportunities around the management of urban space. Through the processes that have been the object of study, this research analyzes the successes and failures over the last five years of alternative management of vacant spaces, seeking to extract formulas that are likely to join the current way of making city. The focus of this urban study is the interpretation of public concepts, considered as key dimensions, not obliterating the other forms of urban space, but trying to make an in-depth analysis of this fragment within the global urban concept. Other activities intrinsically associated to public space generation, such as art, philosophy, anthropology or even sociology, are also contributing to this research. This interdisciplinary approach tries to enrich the research by recognizing the informal elements participating in emergent public management processes. The ex profeso devised methodology is structured by three main strategies: governance, complexity and Social Cohesiveness. Governance considers elements associated to informality, transversal dynamics, appropriation, participation, transparency and networking. Complexity encompasses elements of urban diversity, sustainable usage of public space, reactivation, urban space production, urban ecology and creative processes. Social Cohesiveness includes elements for equipment innovation, bottom-up processes, rhizome, identity, liquid systems and empowerment. This analyzing machine is tested on three urban scenarios: the urban scene, container buildings and empty spaces. Five relevant urban situations in Madrid have been selected, all of them developed in last five years, thus establishing the basis for other experiences of informal urban management. The result of the research, confirms the relevance of additional dimensions to traditional approaches for urban development. The urban space is recognized as a situational container of public sense and a potential multiplier of functional effects such as public management, temporality, participation, rehabilitation, multiplicity of uses, correction of compactness; perceptual and esthetic effects on the urban scene; politic effects, training, empowerment; social effects as generating new networks and identity creation. To sum up, the purpose of this thesis is to share the conclusions obtained by evaluating reference scenarios that could be applied in similar processes for cities and urban environment management and planning.

A CONCEPÇÃO DE DOCÊNCIA NO INSTITUTO DE QUÍMICA DA UNIVERSIDADE DE SÃO PAULO: PROFESSOR OU PESQUISADOR?

Este estudo tem a finalidade de contribuir para a compreensão da concepção de docência que se articulou em um dos espaços de uma das maiores universidades brasileiras, a Universidade de São Paulo, ou seja, o Instituto de Química, conhecido como IQ-USP. Nessa perspectiva, o IQ-USP é, portanto, destacado como o objeto de estudo desta pesquisa, uma vez que sua história se entrelaça com a própria criação da Universidade e seu paradigma científico está centrado no perfil de análise determinado por este trabalho: a área de conhecimento das ciências exatas. Partindo do pressuposto que a concepção de como se deve constituir o ensino superior está intrinsecamente relacionada com a visão de mundo, de conhecimento e de educação elaborada pela própria trajetória histórica da universidade, mas também pelas relações que esta estabelece com a comunidade, durante todo o seu processo de ação , é possível dizer que tais crenças e valores, selecionados e hierarquizados pela comunidade acadêmica, acabam por intervir na formação específica de seus professores. Destaca-se, assim, sob o olhar da pesquisa qualitativa, o estudo a respeito da trajetória de formação do profissional docente que se constitui ao longo da história da própria Universidade em que esse está inserido e que subsidia a sua concepção de ser docente. Nessa perspectiva, alguns autores trazem muitas contribuições para o esclarecimento da concepção de docência implícita na formação do professor universitário e seus reflexos na prática docente cotidiana. Entre estes autores, destacamos o pensamento de Paschoal Senise (2006), Maria Isabel da Cunha (2007), Heladio César G. Antunha (1974) e J. Gimeno Sacristán (1998 e 1999). A coleta de dados foi realizada utilizando-se documentos históricos e informativos, como também entrevistas semi-estruturadas, em uma abordagem sempre qualitativa, uma vez que esta nos fornece melhores condições de entendimento dos aspectos subjetivos de que se reveste a problemática da pesquisa. Fundamentado nos dados levantados e analisados à luz da contribuição teórica dos autores referenciados neste trabalho, reforçamos a conclusão de que a instituição faz o profissional, evidenciando-se na formação do docente do IQ-USP a tradição e a inovação, dialeticamente, caminhando juntas.(AU)

A CONCEPÇÃO DE DOCÊNCIA NO INSTITUTO DE QUÍMICA DA UNIVERSIDADE DE SÃO PAULO: PROFESSOR OU PESQUISADOR?

Este estudo tem a finalidade de contribuir para a compreensão da concepção de docência que se articulou em um dos espaços de uma das maiores universidades brasileiras, a Universidade de São Paulo, ou seja, o Instituto de Química, conhecido como IQ-USP. Nessa perspectiva, o IQ-USP é, portanto, destacado como o objeto de estudo desta pesquisa, uma vez que sua história se entrelaça com a própria criação da Universidade e seu paradigma científico está centrado no perfil de análise determinado por este trabalho: a área de conhecimento das ciências exatas. Partindo do pressuposto que a concepção de como se deve constituir o ensino superior está intrinsecamente relacionada com a visão de mundo, de conhecimento e de educação elaborada pela própria trajetória histórica da universidade, mas também pelas relações que esta estabelece com a comunidade, durante todo o seu processo de ação , é possível dizer que tais crenças e valores, selecionados e hierarquizados pela comunidade acadêmica, acabam por intervir na formação específica de seus professores. Destaca-se, assim, sob o olhar da pesquisa qualitativa, o estudo a respeito da trajetória de formação do profissional docente que se constitui ao longo da história da própria Universidade em que esse está inserido e que subsidia a sua concepção de ser docente. Nessa perspectiva, alguns autores trazem muitas contribuições para o esclarecimento da concepção de docência implícita na formação do professor universitário e seus reflexos na prática docente cotidiana. Entre estes autores, destacamos o pensamento de Paschoal Senise (2006), Maria Isabel da Cunha (2007), Heladio César G. Antunha (1974) e J. Gimeno Sacristán (1998 e 1999). A coleta de dados foi realizada utilizando-se documentos históricos e informativos, como também entrevistas semi-estruturadas, em uma abordagem sempre qualitativa, uma vez que esta nos fornece melhores condições de entendimento dos aspectos subjetivos de que se reveste a problemática da pesquisa. Fundamentado nos dados levantados e analisados à luz da contribuição teórica dos autores referenciados neste trabalho, reforçamos a conclusão de que a instituição faz o profissional, evidenciando-se na formação do docente do IQ-USP a tradição e a inovação, dialeticamente, caminhando juntas.(AU)

WEBJORNALISMO COLABORATIVO - A PRESENÇA DOS USUÁRIOS NO CONTEÚDO INFORMATIVO DO PORTAL R7

Este estudo procura verificar como ocorre a colaboração dos usuários no conteúdo informativo do Portal R7, a partir da nova configuração da internet, a web 2.0, criada em 2004. O termo web 2.0 surgiu para qualificar uma segunda geração de comunidades e serviços, em um ambiente de interação e participação que engloba diversas linguagens. Com o crescimento da adesão à tecnologia digital, algumas barreiras que limitavam a colaboração nos conteúdos informativos foram superadas e o ambiente comunicacional tornou-se um espaço de intercâmbio para experiências e práticas do cotidiano. Nesse cenário, os internautas passam a ter uma relação mais aproximativa nos processos midiáticos presentes no suporte digital, no qual o cidadão pode se expressar, ter maior visibilidade e se relacionar a partir do momento em que ele produz, publica e compartilha qualquer tipo de conteúdo, seja de caráter informativo ou de entretenimento. A revisão bibliográfica abrangeu autores como Ciro Marcondes Filho, José Marques de Melo, Nelson Traquina, Alex Primo, Ana Brambilla, Marcelo Träsel, Raquel Recuero, Polyana Ferrari, Squirra, entre outros. O método de investigação utilizado é o qualitativo, por meio de uma pesquisa exploratória descritiva, do tipo estudo de caso. Os instrumentos para a investigação foram a observação direta assistemática e a entrevista semiestruturada (ou semiaberta). O principal resultado obtido é que o webjornalismo colaborativo no Portal R7 é prioritariamente induzido pelas redes sociais, especialmente o Facebook e o Twitter, inspirado no “call for action”, como estratégia para chamar à colaboração. As práticas jornalísticas estão intrinsicamente dependentes da ação do usuário, sendo que o jornalista agrega às práticas de checagem uma nova etapa, a de relacionamento com o usuário do Portal, para agregar e fidelizar a audiência, valorizando a colaboração em todas as etapas de produção.

Context-sensitive synaptic plasticity and temporal-to-spatial transformations in hippocampal slices

Hippocampal slices are used to show that, as a temporal input pattern of activity flows through a neuronal layer, a temporal-to-spatial transformation takes place. That is, neurons can respond selectively to the first or second of a pair of input pulses, thus transforming different temporal patterns of activity into the activity of different neurons. This is demonstrated using associative long-term potentiation of polysynaptic CA1 responses as an activity-dependent marker: by depolarizing a postsynaptic CA1 neuron exclusively with the first or second of a pair of pulses from the dentate gyrus, it is possible to “tag” different subpopulations of CA3 neurons. This technique allows sampling of a population of neurons without recording simultaneously from multiple neurons. Furthermore, it reflects a biologically plausible mechanism by which single neurons may develop selective responses to time-varying stimuli and permits the induction of context-sensitive synaptic plasticity. These experimental results support the view that networks of neurons are intrinsically able to process temporal information and that it is not necessary to invoke the existence of internal clocks or delay lines for temporal processing on the time scale of tens to hundreds of milliseconds.

Decoding temporally encoded sensory input by cortical oscillations and thalamic phase comparators

The temporally encoded information obtained by vibrissal touch could be decoded “passively,” involving only input-driven elements, or “actively,” utilizing intrinsically driven oscillators. A previous study suggested that the trigeminal somatosensory system of rats does not obey the bottom-up order of activation predicted by passive decoding. Thus, we have tested whether this system obeys the predictions of active decoding. We have studied cortical single units in the somatosensory cortices of anesthetized rats and guinea pigs and found that about a quarter of them exhibit clear spontaneous oscillations, many of them around whisking frequencies (≈10 Hz). The frequencies of these oscillations could be controlled locally by glutamate. These oscillations could be forced to track the frequency of induced rhythmic whisker movements at a stable, frequency-dependent, phase difference. During these stimulations, the response intensities of multiunits at the thalamic recipient layers of the cortex decreased, and their latencies increased, with increasing input frequency. These observations are consistent with thalamocortical loops implementing phase-locked loops, circuits that are most efficient in decoding temporally encoded information like that obtained by active vibrissal touch. According to this model, and consistent with our results, populations of thalamic “relay” neurons function as phase “comparators” that compare cortical timing expectations with the actual input timing and represent the difference by their population output rate.

Dynamics of fluorescence fluctuations in green fluorescent protein observed by fluorescence correlation spectroscopy

We have investigated the pH dependence of the dynamics of conformational fluctuations of green fluorescent protein mutants EGFP (F64L/S65T) and GFP-S65T in small ensembles of molecules in solution by using fluorescence correlation spectroscopy (FCS). FCS utilizes time-resolved measurements of fluctuations in the molecular fluorescence emission for determination of the intrinsic dynamics and thermodynamics of all processes that affect the fluorescence. Fluorescence excitation of a bulk solution of EGFP decreases to zero at low pH (pKa = 5.8) paralleled by a decrease of the absorption at 488 nm and an increase at 400 nm. Protonation of the hydroxyl group of Tyr-66, which is part of the chromophore, induces these changes. When FCS is used the fluctuations in the protonation state of the chromophore are time resolved. The autocorrelation function of fluorescence emission shows contributions from two chemical relaxation processes as well as diffusional concentration fluctuations. The time constant of the fast, pH-dependent chemical process decreases with pH from 300 μs at pH 7 to 45 μs at pH 5, while the time-average fraction of molecules in a nonfluorescent state increases to 80% in the same range. A second, pH-independent, process with a time constant of 340 μs and an associated fraction of 13% nonfluorescent molecules is observed between pH 8 and 11, possibly representing an internal proton transfer process and associated conformational rearrangements. The FCS data provide direct measures of the dynamics and the equilibrium properties of the protonation processes. Thus FCS is a convenient, intrinsically calibrated method for pH measurements in subfemtoliter volumes with nanomolar concentrations of EGFP.

Protective anti-tumor immunity induced by vaccination with recombinant adenoviruses encoding multiple tumor-associated cytotoxic T lymphocyte epitopes in a string-of-beads fashion

Vaccines harboring genes that encode functional oncoproteins are intrinsically hazardous, as their application may lead to introduction of these genes into normal cells and thereby to tumorigenesis. On the other hand, oncoproteins are especially attractive targets for immunotherapy of cancer, as their expression is generally required for tumor growth, making the arisal of tumor variants lacking these antigens unlikely. Using murine tumor models, we investigated the efficacy of polyepitope recombinant adenovirus (rAd) vaccines, which encode only the immunogenic T cell epitopes derived from several oncogenes, for the induction of protective anti-tumor immunity. We chose to employ rAd, as these are safe vectors that do not induce the side effects associated with, for example, vaccinia virus vaccines. A single polyepitope rAd was shown to give rise to presentation of both H-2 and human leukocyte antigen-restricted cytotoxic T lymphocyte (CTL) epitopes. Moreover, vaccination with a rAd encoding H-2-restricted CTL epitopes, derived from human adenovirus type 5 early region 1 and human papilloma virus type 16-induced tumors, elicited strong tumor-reactive CTL and protected the vaccinated animals against an otherwise lethal challenge with either of these tumors. The protection induced was superior compared with that obtained by vaccination with irradiated tumor cells. Thus, vaccination with polyepitope rAd is a powerful approach for the induction of protective anti-tumor immunity that allows simultaneous immunization against multiple tumor-associated T cell epitopes, restricted by various major histocompatibility complex haplotypes.

Slow and fast dietary proteins differently modulate postprandial protein accretion

The speed of absorption of dietary amino acids by the gut varies according to the type of ingested dietary protein. This could affect postprandial protein synthesis, breakdown, and deposition. To test this hypothesis, two intrinsically 13C-leucine-labeled milk proteins, casein (CAS) and whey protein (WP), of different physicochemical properties were ingested as one single meal by healthy adults. Postprandial whole body leucine kinetics were assessed by using a dual tracer methodology. WP induced a dramatic but short increase of plasma amino acids. CAS induced a prolonged plateau of moderate hyperaminoacidemia, probably because of a slow gastric emptying. Whole body protein breakdown was inhibited by 34% after CAS ingestion but not after WP ingestion. Postprandial protein synthesis was stimulated by 68% with the WP meal and to a lesser extent (+31%) with the CAS meal. Postprandial whole body leucine oxidation over 7 h was lower with CAS (272 ± 91 μmol⋅kg−1) than with WP (373 ± 56 μmol⋅kg−1). Leucine intake was identical in both meals (380 μmol⋅kg−1). Therefore, net leucine balance over the 7 h after the meal was more positive with CAS than with WP (P < 0.05, WP vs. CAS). In conclusion, the speed of protein digestion and amino acid absorption from the gut has a major effect on whole body protein anabolism after one single meal. By analogy with carbohydrate metabolism, slow and fast proteins modulate the postprandial metabolic response, a concept to be applied to wasting situations.

Hypoxic Regulation of Vascular Endothelial Growth Factor mRNA Stability Requires the Cooperation of Multiple RNA Elements

Vascular endothelial growth factor (VEGF) is a key regulator of developmental, physiological, and tumor angiogenesis. Upregulation of VEGF expression by hypoxia appears to be a critical step in the neovascularization of solid cancers. The VEGF mRNA is intrinsically labile, but in response to hypoxia the mRNA is stabilized. We have systematically analyzed the regions in the VEGF mRNA that are responsible for its lability under normoxic conditions and for stabilization in response to hypoxia. We find that the VEGF mRNA not only contains destabilizing elements in its 3′ untranslated region (3′UTR), but also contains destabilizing elements in the 5′UTR and coding region. Each region can independently promote mRNA degradation, and together they act additively to effect rapid degradation under normoxic conditions. Stabilization of the mRNA in response to hypoxia is completely dependent on the cooperation of elements in each of the 5′UTR, coding region, and 3′UTR. Combinations of any of two of these three regions were completely ineffective in responding to hypoxia, whereas combining all three regions allowed recapitulation of the hypoxic stabilization seen with the endogenous VEGF mRNA. We conclude that multiple regions in the VEGF mRNA cooperate both to ensure the rapid degradation of the mRNA under normoxic conditions and to allow stabilization of the mRNA in response to hypoxia. Our findings highlight the complexity of VEGF gene expression and also reveal a mechanism of gene regulation that could become the target for strategies of therapeutic intervention.

Taxol Suppresses Dynamics of Individual Microtubules in Living Human Tumor Cells

Microtubules are intrinsically dynamic polymers, and their dynamics play a crucial role in mitotic spindle assembly, the mitotic checkpoint, and chromosome movement. We hypothesized that, in living cells, suppression of microtubule dynamics is responsible for the ability of taxol to inhibit mitotic progression and cell proliferation. Using quantitative fluorescence video microscopy, we examined the effects of taxol (30–100 nM) on the dynamics of individual microtubules in two living human tumor cell lines: Caov-3 ovarian adenocarcinoma cells and A-498 kidney carcinoma cells. Taxol accumulated more in Caov-3 cells than in A-498 cells. At equivalent intracellular taxol concentrations, dynamic instability was inhibited similarly in the two cell lines. Microtubule shortening rates were inhibited in Caov-3 cells and in A-498 cells by 32 and 26%, growing rates were inhibited by 24 and 18%, and dynamicity was inhibited by 31 and 63%, respectively. All mitotic spindles were abnormal, and many interphase cells became multinucleate (Caov-3, 30%; A-498, 58%). Taxol blocked cell cycle progress at the metaphase/anaphase transition and inhibited cell proliferation. The results indicate that suppression of microtubule dynamics by taxol deleteriously affects the ability of cancer cells to properly assemble a mitotic spindle, pass the metaphase/anaphase checkpoint, and produce progeny.

BiP and Immunoglobulin Light Chain Cooperate to Control the Folding of Heavy Chain and Ensure the Fidelity of Immunoglobulin Assembly

The immunoglobulin (Ig) molecule is composed of two identical heavy chains and two identical light chains (H2L2). Transport of this heteromeric complex is dependent on the correct assembly of the component parts, which is controlled, in part, by the association of incompletely assembled Ig heavy chains with the endoplasmic reticulum (ER) chaperone, BiP. Although other heavy chain-constant domains interact transiently with BiP, in the absence of light chain synthesis, BiP binds stably to the first constant domain (CH1) of the heavy chain, causing it to be retained in the ER. Using a simplified two-domain Ig heavy chain (VH-CH1), we have determined why BiP remains bound to free heavy chains and how light chains facilitate their transport. We found that in the absence of light chain expression, the CH1 domain neither folds nor forms its intradomain disulfide bond and therefore remains a substrate for BiP. In vivo, light chains are required to facilitate both the folding of the CH1 domain and the release of BiP. In contrast, the addition of ATP to isolated BiP–heavy chain complexes in vitro causes the release of BiP and allows the CH1 domain to fold in the absence of light chains. Therefore, light chains are not intrinsically essential for CH1 domain folding, but play a critical role in removing BiP from the CH1 domain, thereby allowing it to fold and Ig assembly to proceed. These data suggest that the assembly of multimeric protein complexes in the ER is not strictly dependent on the proper folding of individual subunits; rather, assembly can drive the complete folding of protein subunits.